U.S. patent application number 16/552952 was filed with the patent office on 2020-01-30 for ion-conducting membranes.
The applicant listed for this patent is Dioxide Materials, Inc.. Invention is credited to Qingmei Chen, Zengcai Liu, Richard I. Masel, Syed Dawar Sajjad.
Application Number | 20200030787 16/552952 |
Document ID | / |
Family ID | 69177702 |
Filed Date | 2020-01-30 |
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United States Patent
Application |
20200030787 |
Kind Code |
A1 |
Masel; Richard I. ; et
al. |
January 30, 2020 |
Ion-Conducting Membranes
Abstract
An anion-conducting polymeric membrane comprises
vinylbenzyl-R.sub.s vinylbenzyl-R.sub.x and styrene-R.sub.t.
R.sub.s is a positively charged amine or phosphine group. The total
weight of the vinylbenzyl-R.sub.s groups is greater than 15% of the
total weight of the membrane.
Inventors: |
Masel; Richard I.; (Boca
Raton, FL) ; Sajjad; Syed Dawar; (Boca Raton, FL)
; Chen; Qingmei; (Savoy, IL) ; Liu; Zengcai;
(Boca Raton, FL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dioxide Materials, Inc. |
Boca Raton |
FL |
US |
|
|
Family ID: |
69177702 |
Appl. No.: |
16/552952 |
Filed: |
August 27, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15810106 |
Nov 12, 2017 |
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16552952 |
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15400775 |
Jan 6, 2017 |
9849450 |
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15810106 |
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15090477 |
Apr 4, 2016 |
9580824 |
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15400775 |
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14704935 |
May 5, 2015 |
9370773 |
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15090477 |
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PCT/US2015/014328 |
Feb 3, 2015 |
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14704935 |
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PCT/US2015/026507 |
Apr 17, 2015 |
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14704935 |
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62066823 |
Oct 21, 2014 |
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62066823 |
Oct 21, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 8/1039 20130101;
B01D 71/44 20130101; H01M 8/1067 20130101; C02F 1/44 20130101; C08J
2325/08 20130101; H01M 2008/1095 20130101; B01D 2325/42 20130101;
H01M 2300/0082 20130101; B01D 71/76 20130101; C08J 5/2243 20130101;
B01J 41/14 20130101; H01M 8/1023 20130101; B01D 71/28 20130101;
C02F 2201/46115 20130101; C25B 13/08 20130101 |
International
Class: |
B01J 41/14 20060101
B01J041/14; B01D 71/28 20060101 B01D071/28; C25B 13/08 20060101
C25B013/08; H01M 8/1023 20060101 H01M008/1023; H01M 8/1039 20060101
H01M008/1039; H01M 8/1067 20060101 H01M008/1067; C02F 1/44 20060101
C02F001/44; C08J 5/22 20060101 C08J005/22 |
Claims
1. An anion-conducting membrane comprising a polymer comprising the
reaction product of vinylbenzyl-R.sub.s, vinylbenzyl-R.sub.x and
styrene-R.sub.t, wherein: (a) R.sub.s is a positively charged amine
or phosphine group, (b) R.sub.x is independently selected from
OH--, halogens, linear alkyls, branched alkyls, cyclic alkyls,
heteroalkyls, aryls, heteroaryls, alkylaryls, and heteroalkylaryls.
(c) R.sub.t is independently selected from hydrogen, OH--,
halogens, linear alkyls, branched alkyls, cyclic alkyls,
heteroalkyls, aryls, heteroaryls, alkylaryls, and heteroalkylaryls,
(d) R.sub.x is a different chemical species than R.sub.s, (e)
styrene-R.sub.t is a different chemical species than
vinylbenzyl-R.sub.s and vinylbenzyl-R.sub.x, (f) the total weight
of the vinylbenzyl-R.sub.s is at least 10% of the weight of the
polymer, (g) the total weight of the vinylbenzyl-R.sub.x is at
least 1% of the weight of the polymer, (h) the total weight of the
styrene-R.sub.t is at least 1% of the weight of the polymer.
2. The membrane of claim 1, wherein the total weight of
styrene-R.sub.t is at least 10% of the weight of the polymer.
3. The membrane of claim 1, wherein the total weight of
vinylbenzyl-R.sub.x is at least 10% of the weight of the
polymer.
4. The membrane of claim 1, wherein the vinylbenzyl-R.sub.s
comprises the reaction product of benzyl-X, wherein X is a halogen,
with at least one of: 1,2,2,6,6-pentamethylpiperidine,
1,2,2,5,5-pentamethylpyrrolidine, tetramethylimidazole,
triethylamine, tripropylamine, trimethylamine, N-methylpiperdine,
1-ethylpiperidine, piperidine, 1,4'-bipiperidine,
1-methylpyrrolidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine,
1-pyrrolidine ethanamine, 2,3,5-trimethylpyridine,
2,4,6-trimethylpyridine, 2,6-dimethylpyridine,
2,4-dimethylpyridine, 2,3,5-trimethylpyridine,
4-methyl-2-(1-pyrrolyl)pyridine, 2-methylpyridine,
3-methylpyridine, 4-methylpyridine, pyridine, 4,4'-dipyridyl,
2,2'-bipyridyl, tributylamine, N,N-diisopropylethylamine,
triphenylamine, N,N-dimethylcyclohexylamine,
N,N-dicyclohexylmethylamine, triphenylphosphine,
1,2-dimethylindole, indole, 1-methylindole, hexamethylenetetramine,
2,3,5,6-tetramethylpyrazine, 2,3,5-trimethylpyrazine,
2,3-dimethylpyrazine, 3-methylpyridazine, 2-methylpyrazine,
2,3-diethylpyrazine, ethylpyrazine, pyrazine, 1-methylimidazole,
pyrimidine, 4-methylpyrimidine, pyridazine, triazole,
3,5-dimethyl-1,2,4-triazole, 1,2-dimethylimidazole,
2,4,5-triphenylimidazole, 1-decyl-2-methylimidazole,
1-(2-hydroxyethyl)imidazole, guanidine, tetramethyl guanidine,
dipiperidine, dipyridine, ethylenediamine, propylenediamine,
N,N,N'-trimethylethylenediamine, ethylenediaminetetraacetic acid,
alkyldiamines, other diamines, ethanolamine, triethanolamine,
methylethanolamine, dimethylethanolamine, propanolamine,
3-butenylmagnesium, isobutylmagnesium bromide, cyclohexylmagnesium
chloride, and amino acid.
5. The membrane of claim 4, wherein vinylbenzyl-R.sub.x comprises
at least one of: (i) benzyl-OH, (ii) benzyl-X, wherein X is a
halogen, (iii) benzyl crosslinked to vinylbenzyl-R.sub.s,
styrene-R.sub.t or a different vinylbenzyl-R.sub.x, (iv) the
reaction product of benzyl-X with at least one of:
1,2,2,6,6-pentamethylpiperidine, 1,2,2,5,5-pentamethylpyrrolidine,
tetramethylimidazole, triethylamine, tripropylamine,
trimethylamine, N-methylpiperdine, 1-ethylpiperidine, piperidine,
1,4'-bipiperidine, 1-methylpyrrolidine,
2,2,6,6-tetramethylpiperidine, pyrrolidine, 1-pyrrolidine
ethanamine, 2,3,5-trimethylpyridine, 2,4,6-trimethylpyridine,
2,6-dimethylpyridine, 2,4-dimethylpyridine,
2,3,5-trimethylpyridine, 4-methyl-2-(1-pyrrolyl)pyridine,
2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyridine,
4,4'-dipyridyl, 2,2'-bipyridyl, tributylamine,
N,N-diisopropylethylamine, triphenylamine,
N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine,
triphenylphosphine, 1,2-dimethylindole, indole, 1-methylindole,
hexamethylenetetramine, 2,3,5,6-tetramethylpyrazine,
2,3,5-trimethylpyrazine, 2,3-dimethylpyrazine, 3-methylpyridazine,
2-methylpyrazine, 2,3-diethylpyrazine, ethylpyrazine, pyrazine,
1-methylimidazole, pyrimidine, 4-methylpyrimidine, pyridazine,
triazole, 3,5-dimethyl-1,2,4-triazole, 1,2-dimethylimidazole,
2,4,5-triphenylimidazole, 1-decyl-2-methylimidazole,
1-(2-hydroxyethyl)imidazole, guanidine, tetramethyl guanidine,
dipiperidine, dipyridine, ethylenediamine, propylenediamine,
N,N,N'-trimethylethylenediamine, ethylenediaminetetraacetic acid,
alkyldiamines, other diamines, ethanolamine, triethanolamine,
methylethanolamine, dimethylethanolamine, propanolamine,
3-butenylmagnesium, isobutylmagnesium bromide, cyclohexylmagnesium
chloride, and amino acid.
6. The membrane of claim 5, wherein at least one of R.sub.s, and
R.sub.x are not positively charged cyclic amines, Cl or OH.
7. The membrane of claim 6, wherein both R.sub.s, and R.sub.x are
not positively charged cyclic amines, Cl or OH.
8. The membrane of claim 1, wherein R.sub.t is hydrogen or a linear
alkyl.
9. The polymer in claim 2, wherein the polymer has a molecular
weight between 1000 and 10,000,000 atomic units (A.U.)
10. The membrane of claim 1, wherein the membrane thickness is
between 10-300 micrometers.
11. The membrane of claim 1, wherein the membrane has an area
specific resistance of 0.1 ohm-cm.sup.2 or less.
12. A battery, fuel cell, electrolyzer, water purification system
or CO.sub.2 capture system comprising the membrane of claim 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation in part of U.S.
patent application Ser. No. 15/810,106 filed on Nov. 12, 2017,
entitled "Ion-Conducting Membranes". The '106 patent is, in turn, a
continuation-in-part of U.S. patent application Ser. No. 15/400,775
filed on Jan. 6, 2017 (now U.S. Pat. No. 9,849,450 issued on Dec.
26, 2017), also entitled "Ion-Conducting Membranes". The '775
application is, in turn, a continuation in part of U.S. patent
application Ser. No. 15/090,477 filed on Apr. 4, 2016 (now U.S.
Pat. No. 9,580,824 issued on Feb. 28, 2017), also entitled
"Ion-Conducting Membranes". The '477 application is, in turn, a
continuation-in-part of U.S. patent application Ser. No. 14/704,935
filed on May 5, 2015, also entitled "Ion-Conducting Membranes" (now
U.S. Pat. No. 9,370,773 issued on Jun. 21, 2016). The '935
application was, in turn, a continuation-in-part of International
Application No. PCT/US2015/14328, filed on Feb. 3, 2015, entitled
"Electrolyzer and Membranes". The '328 international application
claimed priority benefits, in turn, from U.S. provisional patent
application Ser. No. 62/066,823, filed on Oct. 21, 2014.
[0002] The '935 application was also a continuation-in-part of
International Application No. PCT/US2015/26507 filed on Apr. 17,
2015, entitled "Electrolyzer and Membranes". The '507 international
application also claimed priority benefits, in turn, from U.S.
provisional patent application Ser. No. 62/066,823 filed on Oct.
21, 2014.
[0003] The '106 parent application, the '775 application, the '477
application, the '935 application, the '823 provisional
application, and the '328 and '507 international applications are
each hereby incorporated by reference herein in their entirety.
[0004] This application is also related to U.S. patent application
Ser. No. 14/035,935 filed on Sep. 24, 2013, entitled "Devices and
Processes for Carbon Dioxide Conversion into Useful Fuels and
Chemicals" (now U.S. Pat. No. 9,370,733; U.S. patent application
Ser. No. 12/830,338 filed on Jul. 4, 2010, entitled "Novel Catalyst
Mixtures"; International application No. PCT/2011/030098 filed Mar.
25, 2011, entitled "Novel Catalyst Mixtures"; U.S. patent
application Ser. No. 13/174,365 filed on Jun. 30, 2011, entitled
"Novel Catalyst Mixtures"; International application No.
PCT/US2011/042809 filed Jul. 1, 2011, entitled "Novel Catalyst
Mixtures"; U.S. patent application Ser. No. 13/530,058 filed on
Jun. 21, 2012, entitled "Sensors for Carbon Dioxide and Other End
Uses"; International application No. PCT/US2012/043651 filed on
Jun. 22, 2012, entitled "Low Cost Carbon Dioxide Sensors"; and U.S.
patent application Ser. No. 13/445,887 filed on Apr. 12, 2012,
entitled "Electrocatalysts for Carbon Dioxide Conversion".
FIELD OF THE INVENTION
[0005] The field of the invention is electrochemistry. The
compositions and membranes are useful for the electrolysis of water
and carbon dioxide, batteries, electric power generation using fuel
cells, water purification and carbon dioxide capture systems.
BACKGROUND OF THE INVENTION
[0006] U.S. Pat. Nos. 9,370,773, 9,481,939, 9,580,824, 9,815,021,
9,849,450, 9,943,841, 9,945,040, 9,957,624, 9,982,353, 10,047,446,
10,147,974, 10,173,169, and U.S. patent application Ser. Nos.
15/810,106, 15/908,325, 15/922,883, 15/967,293, 16/024,827,
16/164,289, 16/238,425, and 16/429,868 (Masel et al.) disclose a
number of ion conducting membranes. These membranes were optimized
for carbon dioxide electrolysis.
[0007] Disclosed herein are membranes that are useful, if not
superior, for the electrolysis of water, batteries, electric power
generation using fuel cells, and water purification and carbon
dioxide capture systems.
SUMMARY OF THE INVENTION
[0008] An anion-conducting membrane comprising a polymer comprising
the reaction products of vinylbenzyl-R.sub.s, vinylbenzyl-R.sub.x
and styrene-R.sub.t wherein [0009] (a) R.sub.s is a positively
charged amine group or phosphene [0010] (b) R.sub.x is
independently selected from OH--, halogens, linear alkyls, branched
alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls,
alkylaryls, heteroalkylaryls or polymers thereof. [0011] (c)
R.sub.t is independently selected from hydrogen, OH--, halogens,
linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls,
heteroaryls, alkylaryls, and heteroalkylaryls. [0012] (d) R.sub.x
is a different chemical species than R.sub.s [0013] (e)
styrene-R.sub.t is a different chemical species than
vinylbenzyl-R.sub.s and vinylbenzyl-R.sub.x [0014] (f) the total
weight of the vinylbenzyl-R.sub.s is at least 10% of the weight of
the polymer [0015] (g) the total weight of the vinylbenzyl-R.sub.x
is at least 1% of the weight of the polymer [0016] (h) the total
weight of the styrene-R.sub.t is at least 1% of the weight of the
polymer.
[0017] In a preferred embodiment the total weight of the
styrene-R.sub.t is at least 10% of the weight of the polymer.
[0018] In a preferred embodiment, vinylbenzyl-R.sub.s comprises the
reaction product of a benzyl-X, wherein X is a halogen, with at
least one of: 1,2,2,6,6-pentamethylpiperidine,
1,2,2,5,5-pentamethylpyrrolidine, tetramethylimidazole,
triethylamine, tripropylamine, trimethylamine, N-methylpiperdine,
1-ethylpiperidine, piperidine, 1,4'-bipiperidine,
1-methylpyrrolidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine,
1-pyrrolidine ethanamine, 2,3,5-trimethylpyridine,
2,4,6-trimethylpyridine, 2,6-dimethylpyridine,
2,4-dimethylpyridine, 2,3,5-trimethylpyridine,
4-methyl-2-(1-pyrrolyl)pyridine, 2-methylpyridine,
3-methylpyridine, 4-methylpyridine, pyridine, 4,4'-dipyridyl,
2,2'-bipyridyl, tributylamine, N,N-diisopropylethylamine,
triphenylamine, N,N-dimethylcyclohexylamine,
N,N-dicyclohexylmethylamine, triphenylphosphine,
1,2-dimethylindole, indole, 1-methylindole, hexamethylenetetramine,
2,3,5,6-tetramethylpyrazine, 2,3,5-trimethylpyrazine,
2,3-dimethylpyrazine, 3-methylpyridazine, 2-methylpyrazine,
2,3-diethylpyrazine, ethylpyrazine, pyrazine, 1-methylimidazole,
pyrimidine, 4-methylpyrimidine, pyridazine, triazole,
3,5-dimethyl-1,2,4-triazole, 1,2-dimethylimidazole,
2,4,5-triphenylimidazole, 1-decyl-2-methylimidazole,
1-(2-hydroxyethyl)imidazole, guanidine, tetramethyl guanidine,
dipiperidine, dipyridine, ethylenediamine, propylenediamine,
N,N,N'-trimethylethylenediamine, ethylenediaminetetraacetic acid,
alkyldiamines, other diamines, ethanolamine, triethanolamine,
methylethanolamine, dimethylethanolamine, propanolamine,
3-butenylmagnesium, isobutylmagnesium bromide, cyclohexylmagnesium
chloride, and amino acid.
[0019] In a preferred embodiment, vinylbenzyl-R.sub.x comprises at
least one of: (i) benzyl-OH, (ii) benzyl-X, wherein X is a halide,
(iii) a benzyl crosslinked to vinylbenzyl-R.sub.s, styrene-R.sub.t
or a different vinylbenzyl-R.sub.x, and (iv) the reaction product
of a benzyl-X with at least one of:
1,2,2,6,6-pentamethylpiperidine, 1,2,2,5,5-pentamethylpyrrolidine,
tetramethylimidazole, triethylamine, tripropylamine,
trimethylamine, N-methylpiperdine, 1-ethylpiperidine, piperidine,
1,4'-bipiperidine, 1-methylpyrrolidine,
2,2,6,6-tetramethylpiperidine, pyrrolidine, 1-pyrrolidine
ethanamine, 2,3,5-trimethylpyridine, 2,4,6-trimethylpyridine,
2,6-dimethylpyridine, 2,4-dimethylpyridine,
2,3,5-trimethylpyridine, 4-methyl-2-(1-pyrrolyl)pyridine,
2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyridine,
4,4'-dipyridyl, 2,2'-bipyridyl, tributylamine,
N,N-diisopropylethylamine, triphenylamine,
N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine,
triphenylphosphine, 1,2-dimethylindole, indole, 1-methylindole,
hexamethylenetetramine, 2,3,5,6-tetramethylpyrazine,
2,3,5-trimethylpyrazine, 2,3-dimethylpyrazine, 3-methylpyridazine,
2-methylpyrazine, 2,3-diethylpyrazine, ethylpyrazine, pyrazine,
1-methylimidazole, pyrimidine, 4-methylpyrimidine, pyridazine,
triazole, 3,5-dimethyl-1,2,4-triazole, 1,2-dimethylimidazole,
2,4,5-triphenylimidazole, 1-decyl-2-methylimidazole,
1-(2-hydroxyethyl)imidazole, guanidine, tetramethyl guanidine,
dipiperidine, dipyridine, ethylenediamine, propylenediamine,
N,N,N'-trimethylethylenediamine, ethylenediaminetetraacetic acid,
alkyldiamines, other diamines, ethanolamine, triethanolamine,
methylethanolamine, dimethylethanolamine, propanolamine,
3-butenylmagnesium, isobutylmagnesium bromide, cyclohexylmagnesium
chloride, and amino acid.
[0020] In an alternate embodiment at least one of R.sub.s, and
R.sub.x are not positively charged cyclic amines, Cl or OH.
[0021] In an alternate embodiment both R.sub.s, and R.sub.x are not
positively charged cyclic amines, Cl or OH.
[0022] In an alternate embodiment R.sub.s, R.sub.t and R.sub.x are
each not positively charged cyclic amines, Cl or OH.
[0023] In a preferred embodiment Vinylbenzyl-R.sub.x and
Styrene-R.sub.t are not divinylbenzene.
[0024] In a preferred embodiment R.sub.t is a hydrogen or a linear
alkyl.
[0025] In a preferred embodiment, the polymer will have a molecular
weight between 1000 and 10,000,000 atomic units (A.U.) preferably
between 10,000 and 1,000,000 A.U., most preferably between 25,000
and 250,000 A.U.
[0026] In a preferred embodiment, the polymeric composition is in
the form of a membrane. The membrane has a preferred thickness of
10-300 micrometers.
[0027] In a preferred embodiment the membrane has an area specific
resistance of 0.1 ohm-cm.sup.2 or less.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENT(S)
[0028] It is understood that the process is not limited to the
particular methodology, protocols and reagents described herein, as
these can vary as persons familiar with the technology involved
here will recognize. It is also to be understood that the
terminology used herein is used for the purpose of describing
particular embodiments only, and is not intended to limit the scope
of the process. It also is to be noted that as used herein and in
the appended claims, the singular forms "a," "an," and "the"
include the plural reference unless the context clearly dictates
otherwise. Thus, for example, a reference to "a linker" is a
reference to one or more linkers and equivalents thereof known to
those skilled in the art. Similarly, the phrase "and/or" is used to
indicate one or both stated cases can occur, for example, A and/or
B includes (A and B) and (A or B).
[0029] Unless defined otherwise, technical and scientific terms
used herein have the same meanings as commonly understood by one of
ordinary skill in the art to which the process pertains. The
embodiments of the process and the various features and
advantageous details thereof are explained more fully with
reference to the non-limiting embodiments and/or illustrated in the
accompanying drawings and detailed in the following description. It
should be noted that the features illustrated in the drawings are
not necessarily drawn to scale, and features of one embodiment can
be employed with other embodiments as the skilled artisan would
recognize, even if not explicitly stated herein.
[0030] Any numerical value ranges recited herein include all values
from the lower value to the upper value in increments of one unit,
provided that there is a separation of at least two units between
any lower value and any higher value. As an example, if it is
stated that the concentration of a component or value of a process
variable such as, for example, size, angle size, pressure, time and
the like, is, for example, from 1 to 98, specifically from 20 to
80, more specifically from 30 to 70, it is intended that values
such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, and the like, are
expressly enumerated in this specification. For values which are
less than one, one unit is considered to be 0.0001, 0.001, 0.01 or
0.1 as appropriate. These are only examples of what is specifically
intended and all possible combinations of numerical values between
the lowest value and the highest value are to be treated in a
similar manner.
[0031] Moreover, provided immediately below is a "Definitions"
section, where certain terms related to the process are defined
specifically. Particular methods, devices, and materials are
described, although any methods and materials similar or equivalent
to those described herein can be used in the practice or testing of
the process.
Definitions
[0032] The term "polymer electrolyte membrane" as used here refers
to both cation exchange membranes, which generally comprise
polymers having multiple covalently attached negatively charged
groups, and anion exchange membranes, which generally comprise
polymers having multiple covalently attached positively charged
groups. Typical cation exchange membranes include proton conducting
membranes, such as the perfluorosulfonic acid polymer available
under the trade designation NAFION from E. I. du Pont de Nemours
and Company (DuPont) of Wilmington, Del.
[0033] The term "anion exchange membrane electrolyzer" as used here
refers to an electrolyzer with an anion-conducting polymer
electrolyte membrane separating the anode from the cathode.
[0034] The term "EMIM" as used here refers to
1-ethyl-3-methylimidazolium cations.
[0035] The Term "CV" refers to cyclic voltammetry.
[0036] The term "Millipore water" is water that is produced by a
Millipore filtration system with a resistivity of at least 18.2
megaohm-cm.
[0037] The term "imidazolium" as used here refers to a positively
charged ligand containing an imidazole group. This includes a bare
imidazole or a substituted imidazole. Ligands of the form:
##STR00001##
where R.sub.1-R.sub.5 are each independently selected from
hydrogen, halides linear alkyls, branched alkyls, cyclic alkyls,
heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and
polymers thereof, such as the vinyl benzyl copolymers described
herein, are specifically included.
[0038] The term "pyridinium" as used here refers to a positively
charged ligand containing a pyridine group. This includes a bare
pyridine or a substituted pyridine. Ligands of the form:
##STR00002##
where R.sub.6-R.sub.11 are each independently selected from
hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls,
heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and
polymers thereof, such as the vinyl benzyl copolymers described
herein, are specifically included.
[0039] The term "phosphonium" as used here refers to a positively
charged ligand containing phosphorous. This includes substituted
phosphorous. Ligands of the form:
P.sup.+(R.sub.12R.sub.13R.sub.14R.sub.15)
where R.sub.12-R.sub.15 are each independently selected from
hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls,
heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and
polymers thereof, such as the vinyl benzyl copolymers described
herein, are specifically included.
[0040] The term "positively charged cyclic amine" as used here
refers to a positively charged ligand containing a cyclic amine.
This specifically includes imidazoliums, pyridiniums, pyrazoliums,
pyrrolidiniums, pyrroliums, pyrimidiums, piperidiniums, indoliums,
triaziniums, and polymers thereof, such as the vinyl benzyl
copolymers described herein, are specifically included.
[0041] The term "simple amine" as used here refers to a species of
the form
N(R.sub.16R.sub.17R.sub.18),
wherein R.sub.16, R.sub.17 and R.sub.18 are each independently
selected from hydrogen, linear alkyls, branched alkyls, cyclic
alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls,
heteroalkylaryls, but not polymers.
[0042] The term "substituted ethene" as used here refers to a
monomer of the form:
##STR00003##
wherein R.sub.1-R.sub.4 are each independently selected from
hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls,
heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls,
including polymers.
[0043] The term "water purification system" as used here refers to
a device that removes unwanted constituents from water and, in the
case of a membrane-based device, one that employs a membrane as a
barrier that allows certain substances to pass through while
blocking others.
[0044] The term "battery" as used here refers to a device that
generates electricity via an electrochemical reaction between
substances stored internally within the battery.
[0045] The term "fuel cell" as used here refers to a device that
generates electricity via an electrochemical reaction between
substances that are supplied to the fuel cell from an external
source.
[0046] The term "electrolyzer" as used here refers to an
electrochemical device that uses electrical energy to convert a
substance into constituent substances. In the case of a water
electrolyzer, the device uses electricity to convert water into
hydrogen and oxygen.
[0047] The term "CO.sub.2 capture system" as used here refers to a
device that is able to separate CO.sub.2 from a gas or liquid
stream.
Specific Description
[0048] The examples provided here are merely illustrative and are
not meant to be an exhaustive list of all possible embodiments,
applications or modifications of the present electrochemical
device. Thus, various modifications and variations of the described
methods and systems of the invention will be apparent to those
skilled in the art without departing from the scope of the
invention. Although the invention has been described in connection
with specific embodiments, it should be understood that the
invention as claimed should not be unduly limited to such specific
embodiments. Indeed, various modifications of the described modes
for carrying out the invention which are obvious to those skilled
in the chemical arts or in the relevant fields are intended to be
within the scope of the appended claims.
Specific Example 1: Production of Alternative Membranes
[0049] The objective of this example is to provide a number of
alternate membranes that are useful for the electrolysis of water
and carbon dioxide, batteries, electric power generation using fuel
cells and water purification.
[0050] Generally, the synthesis procedure follows that in U.S. Pat.
No. 9,370,773.
[0051] Step 1: Inhibitor free styrene was prepared by washing
styrene (Sigma Aldrich, Saint Louis, Mo.) with two equal volumes of
7.5% aqueous sodium hydroxide. The inhibitor free styrene was then
washed with four equal volumes of water to make sure it was
neutralized, and was then dried over anhydrous magnesium sulfate.
The tert-butylcatechol (TBC) inhibitor in the vinylbenzyl chloride
(VBC) was removed by extraction with 0.5% potassium hydroxide
solution until a colorless extract was obtained. This extract was
washed with water until neutral and then was dried over anhydrous
magnesium sulfate.
[0052] Step 2: Poly(vinylbenzyl chloride-co-styrene) was then
synthesized by heating a solution of inhibitor free styrene
(Sigma-Aldrich) (10.0581 g, 96.57 mmol) and vinylbenzyl chloride
(Sigma-Aldrich) (6.2323 g, 40.84 mmol) in chlorobenzene
(Sigma-Aldrich) (15 ml) at 60-65.degree. C. in an oil bath for
12-18 hours under argon gas with AIBN
(.alpha.,.alpha.'-Azoisobutyronitrile, Sigma-Aldrich) (0.1613 g,
0.99 wt % based on the total monomers weight) as initiator. The
copolymer was precipitated in ethanol and dried under vacuum.
[0053] Step 3: The resultant copolymer was dissolved in
1-Methoxy-2-propanol (Sigma Aldrich) to form a solution that was
about 30% by weight of polymer.
[0054] Step 4: The solution from step 3 was heated to 60.degree.
C., and 1-Decyl-2-methylimidazole was added and the solution was
continuously stirred for 48 hours.
[0055] Additional polymer solutions were prepared by replacing the
1-Decyl-2-methylimidazole with each of the following compounds:
1,1,3,3-Tetramethylguanidine, 1-Ethylpiperidine,
1-methylpyrrolidine, 2,2'-Bipyridyl, 2,3,5-Trimethylpyridine,
2-Methylpyridine, Pyridine, 3-Methylpyridine, 4,4'-dipyridyl,
4-Methylpyridine, N,N,N',N'-Tetramethyl-1,6-hexanediamine,
N,N-Dicyclohexylmethylamine, 1-(2-hydroxyethyl)imidazole,
N,N-Dimethylcyclohexylamine, N-methyl Piperdine, Tetramethyl
Imidazole, 1-methylimidazole, 1,2-dimethyl imidazole, Tributyl
amine, triethyl amine, Trimethyl amine, Triphenyl phosphine,
Tripropyl amine, 1,3-diaminopropane, Ethylenediamine,
(Methylamino)ethanol, Triethanolamine, Ethanolamine,
Ethylenediaminetetraacetic acid, Trimethylethylenediamine,
3-amino-1-propanol, Piperidine, 1,4'-Bipiperidine,
2,2,6,6-Tetramethylpiperidine, Pyrrolidine, 4,4'-dipyridyl,
Triphenyl amine, 1,2-Dimethylindole, 1-Methylindole,
Hexamethylenetetramine.
[0056] Step 5: Next, an attempt was made to manufacture membranes
from each of the solutions prepared in step 4 by casting them
directly onto a polyethylene terephthalate (PET) liner. The
thickness of the solution on the PET was controlled by a film
applicator (MTI Corporation, Richmond, Calif.) with an adjustable
doctor blade. The membranes were then dried in a vacuum oven at
80.degree. C. for 300 minutes, and then 120.degree. C. for 200
minutes.
[0057] Membranes were successfully prepared from the following
amines: 1,1,3,3-Tetramethylguanidine, 1-Decyl-2-methylimidazole,
1-Ethylpiperidine, 1-methylpyrrolidine, 2,2'-Bipyridyl,
2,3,5-Trimethylpyridine, 2-Methylpyridine, Pyridine,
3-Methylpyridine, 4,4'-dipyridyl, 4-Methylpyridine,
N,N,N',N'-Tetramethyl-1,6-hexanediamine,
N,N-Dicyclohexylmethylamine, 1-(2-hydroxyethyl)imidazole,
N,N-Dimethylcyclohexylamine, N-methyl Piperdine, Tetramethyl
Imidazole, 1-methylimidazole, 1,2-dimethyl imidazole, Tributyl
amine, triethyl amine, Trimethyl amine, Triphenyl phosphine,
Tripropyl amine.
[0058] The solutions made using 1,3-diaminopropane,
Ethylenediamine, (Methylamino)ethanol, Triethanolamine,
Ethanolamine, Ethylenediaminetetraacetic acid,
Trimethylethylenediamine, 3-amino-1-propanol, Piperidine,
1,4'-Bipiperidine, 2,2,6,6-Tetramethylpiperidine, Pyrrolidine,
4,4'-dipyridyl, Triphenyl amine, 1,2-Dimethylindole,
1-Methylindole, Hexamethylenetetramine had too high of a viscosity
to be cast with the MTI casting machine, but it is believed that
they could have been cast using different equipment.
[0059] Nuclear Magnetic Resonance (NMR) indicated that in each case
between 20 and 40% of the vinylbenzyl chloride (VBC) was unreacted,
so that the unreacted VBC represented between 5 and 30% of the
total weight of the membrane.
[0060] Measurements were performed where N,N-Dimethylformamide
(DMF) was substituted for the Dowanol in Step 4. In those cases,
the unreacted VBC was only about 1-3% of the weight of the
polymer.
[0061] The specific area resistance of the each of the membranes
produced in Specific Example 1 was also measured. In all cases the
resultant membranes had an area specific resistance below 0.1
ohm-cm.sup.2 in 1 M KOH so that they are useful as ion conductors
for at least one of: the electrolysis of water, electrolysis of
carbon dioxide, batteries, electric power generation using fuel
cells, water purification, and CO.sub.2 capture systems.
Specific Example 2
[0062] The objective of this example is to show that an
anion-conducting membrane comprising a polymer comprising the
reaction products of vinylbenzyl-R.sub.s, vinylbenzyl-R.sub.x and
styrene-R.sub.t, wherein [0063] (a) R.sub.s is a positively charged
amine or phosphine group, [0064] (b) R.sub.x is independently
selected from linear alkyls, branched alkyls, cyclic alkyls,
heteroalkyls, aryls, heteroaryls, alkylaryls, and heteroalkylaryls,
[0065] (c) R.sub.t is independently selected from linear alkyls,
branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls,
alkylaryls, and heteroalkylaryls, [0066] (d) R.sub.x is a different
chemical species than R.sub.s, also has properties that make the
membrane useful for at least one of: the electrolysis of water and
carbon dioxide, batteries, electric power generation using fuel
cells and water purification.
[0067] First a terpolymer comprising the reaction products styrene,
vinylbenzyl chloride (VBC) and 4-(3-butenyl)styrene was
synthesized. [0068] (a) Reacting VBC with a Grignard reagent
3-Butenylmagnesium bromide (Sigma Aldrich) in tetrahydrofuran (THF)
to yield 4-(3-butenyl)styrene [0069] (b) Mixing 10 grams of
styrene, 3 grams of 4-(3-butenyl)styrene, 1 gram of VBC and 0.14 g
of AIBN in 20 grams of chlorobenzene, and polymerizing as in step 2
of Specific Example 1 above. The resultant polymer was
functionalized with Tetramethyl Imidazole (TMIM) as described in
steps 3 and 4 of Specific Example 1 above, and a membrane was
prepared as described in step 5 of Specific Example 1. This
provided a membrane comprising a copolymer comprising the reaction
products of vinylbenzyl-R.sub.s, vinylbenzyl-R.sub.x and
styrene-R.sub.t where R.sub.s=TMIM, R.sub.x=a linear alkyl, and
R.sub.t=H.
[0070] Polymers with R.sub.x=Branched alkyl, a cyclic alkyl, a
heteroalkyl, an aryl, an alkylaryl and a heteroalkylaryls can be
synthesized in a similar manner by replacing Grignard reagent in
step (a) in the previous paragraph with a Grignard reagent such as
Isobutylmagnesium bromide (Sigma Aldrich), Cyclohexylmagnesium
chloride (Sigma Aldrich), (1,3-Dioxan-2-ylethyl)magnesium bromide
(Sigma Aldrich), 2-Methylbenzylmagnesium chloride (Sigma Aldrich),
Benzylmagnesium chloride (Sigma Aldrich), 3-Methoxybenzylmagnesium
chloride (Sigma Aldrich). Polymers with heteroaryls can be
synthesized using the heteroaryl Grignard reagents disclosed in
Barl, et al. (Heterocycles, Vol. 88, No. 2, 2014, pp. 827-844).
[0071] In a similar manner, polymers where R.sub.t is independently
selected from linear alkyls, branched alkyls, cyclic alkyls,
heteroalkyls, aryls, heteroaryls, alkylaryls, and heteroalkylaryls,
can be manufactured by first creating a styrene-R.sub.t by reacting
VBC with one of the Grignard reagents discussed in the previous
paragraph and then creating a membrane by substituting the
styrene-R.sub.t for styrene in steps 1 to 5 of Specific Example
1.
[0072] The specific area resistance the membrane produced in
Specific Example 2 was also measured. The membrane had an area
specific resistance below 0.1 ohm-cm.sup.2 in 1 M KOH so that it
may be useful for at least one of: the electrolysis of water and
carbon dioxide, batteries, electric power generation using fuel
cells and water purification.
Specific Example 3
[0073] The objective of this example is to show that an
anion-conducting membrane comprising a polymer comprising the
reaction products of vinylbenzyl-R.sub.s, vinylbenzyl-R.sub.x and
styrene-R.sub.t wherein [0074] (a) R.sub.s is a positively charged
amine or phosphine group, [0075] (b) R.sub.x is Cl, OH, or a
crosslink to other parts of the membrane, [0076] (c) R.sub.t is
hydrogen, [0077] (d) R.sub.x is a different chemical species than
R.sub.s, also has properties that make the membrane useful for at
least one of: the electrolysis of water and carbon dioxide,
batteries, electric power generation using fuel cells and water
purification.
[0078] First a PSTMIM membrane was created following the procedure
in specific example 1.
[0079] Next the membrane was soaked in 1 M KOH for 4 hours at room
temperature. NMR as described in U.S. Pat. No. 9,943,841 shows that
the resultant polymer contains benzyl-R.sub.s groups, and
benzyl-R.sub.x groups, R.sub.s=TMIM and R.sub.x=OH. NMR also shows
evidence of crosslinks through the benzyl group.
[0080] The specific area resistance the membrane produced in
Specific Example 3 was also measured. The membrane had an area
specific resistance below 0.1 ohm-cm.sup.2 in 1 M KOH so that it
may be useful for at least one of: the electrolysis of water and
carbon dioxide, batteries, electric power generation using fuel
cells and water purification.
Specific Example 4
[0081] The objective of this example is to provide additional
examples of anion-conducting membranes comprising a polymer
comprising the reaction products of vinylbenzyl-R.sub.s,
vinylbenzyl-R.sub.x and styrene-R.sub.t wherein [0082] (a) R.sub.s
is a positively charged amine or phosphine group, [0083] (b)
R.sub.x is an amine [0084] (c) R.sub.t is hydrogen. [0085] (d)
R.sub.x is a different chemical species than R.sub.s also has
properties that make the membrane useful for at least one of: the
electrolysis of water and carbon dioxide, batteries, electric power
generation using fuel cells and water purification.
[0086] In an alternate synthesis the membrane of Specific Example 1
with R.sub.s=tetramethylimidazole was soaked overnight in an
aqueous solution of one of the following heteroalkyls or
heteroalkylaryls. More specifically the membrane was submerged in
an aqueous solution with 25 ml of water and 3.1 g of one of the
following 1,1,3,3-tetramethylguanidine,
N,N,N'-trimethylethylenediamine, ethylenediaminetetraacetic acid,
ethanol amine, triethanol amine, hexamethylene tetramine, dimethyl
indole and 2,2'-bipyridyl. Only dimethyl indole and 2,2'-bipyridyl
failed to completely dissolve in water due to their lower
solubility. This gave membranes where R.sub.x groups are
heteroalkyls and heteroalkylaryls.
[0087] The specific area resistance of the each of the membranes
produced in Specific Example 4 was also measured. In all cases the
resultant membranes had an area specific resistance below 0.1
ohm-cm.sup.2 in 1 M KOH so that they are useful for at least one
of: the electrolysis of water and carbon dioxide, batteries,
electric power generation using fuel cells and water
purification.
[0088] While particular elements, embodiments and applications of
the present invention have been shown and described, it will be
understood that the invention is not limited thereto since
modifications can be made by those skilled in the art without
departing from the scope of the present disclosure, particularly in
light of the foregoing teachings.
* * * * *